Active agent combinations

ABSTRACT

The novel active compound combinations of
         extracts from seeds of the neem tree and   the active compounds of groups (B) to (F) listed in the description
 
have very good insecticidal and acaricidal properties.

This application is a Divisional application of U.S. application Ser. No. 13/097,508, filed Apr. 29, 2011, which is a Divisional of U.S. application Ser. No. 10/432,979, filed Oct. 3, 2003, now U.S. Pat. No. 7,955,609 issued Jun. 7, 2011, which is a National Stage of PCT/EP01/13340, filed Nov. 19, 2001, which claims priority to German Application 10059606.1, filed Dec. 1, 2000. All of these are hereby incorporated by reference in their entireties.

The present invention relates to novel active compound combinations which comprise, firstly, known extracts from seeds of the neem tree and, secondly, further known pesticidally active compounds, and which have very good insecticidal and acaricidal properties.

It is already known that extracts from the seeds of the neem tree have insecticidal properties (cf. “Römpp Chemie Lexikon”, 9^(th) edition, page 2954, Georg Thieme Verlag, Stuttgart-New York, 1991). The activity of this substance is good; however, it is sometimes unsatisfactory at low application rates.

It is furthermore known that numerous pyrethroids, carbamates, phosphoric acid derivatives and heterocycles can be used for controlling animal pests such as insects and undesirable acarids (cf. WO 93-10 083; DE-A 2 717 040; Farm Chemicals Handbook 1998, C 328; EP-A 0 161 019 and EP-A 0 049 977). However, the activity of these substances is likewise not always satisfactory at low application rates.

It has now been found that the novel active compound combinations comprising

-   A) extracts from seeds of the neem tree     and -   B) an active compound from the group of the pyrethroids, consisting     of     -   (1) cypermethrin,     -   (2) deltamethrin,     -   (3) permethrin,     -   (4) natural pyrethrum,     -   (5) fenpropathrin,     -   (6) cyfluthrin,     -   (7) beta-cyfluthrin and     -   (8) lambda-cyhalothrin,         or -   C) an active compound from the group of the carbamates, consisting     of     -   (9) butocarboxim,     -   (10) pirimicarb,     -   (11) propoxur and     -   (12) methiocarb,         or -   D) a phosphoric acid derivative from the group consisting of     -   (13) isazophos and     -   (14) dimethoate, -   (E) an active compound from the group of the nicotinyls or     neonicotinyls consisting of     -   (15) imidacloprid,     -   (16) thiacloprid,     -   (17) thiamethoxam,     -   (18) acetamiprid and     -   (19) clothianidin,         or -   (F) an active compound from the group consisting of     -   (20) abamectin,     -   (21) diflubenzuron,     -   (22) buprofezin,     -   (23) triflumuron,     -   (24) diafenthiuron,     -   (25) fipronil,     -   (26) spinosad,     -   (27) pymetrozine,     -   (28) cyromazine,     -   (29) dicyclanil,     -   (30) bifenazate,     -   (31) hexathiazox,     -   (32) tebufenpyrad,     -   (33) pyridaben,     -   (34) the ketoenol derivative (I) of the name         3-(2,4-dichlorophenyl)-4-(1,1-dimethyl-propyl-carbonyloxy)-5-spiro-cyclohexyl-3-dihydrofuran-2-one         and     -   (35) the ketoenol derivative (II) of the name         3-(2,4,6-trimethylphenyl)-4-(2,2-dimethyl-propyl-carbonyloxy)-5-spiro-cyclopentyl-3-dihydrofuran-2-one         have very good insecticidal and acaricidal properties.

Surprisingly, the insecticidal and acaricidal activity of the active compound combinations according to the invention is considerably higher than the sum of the activities of the individual active compounds. Thus, an unforeseeable, true synergistic effect is present, and not just an addition of activities.

In the present case, extracts from seeds of the neem tree are to be understood as meaning all customary products which can be isolated from seeds of the neem tree by extraction or squeezing and which contain substantial quantities of azadirachtin. These products include azadirachtin itself.

Various extracts of seeds of the neem tree and azadirachtin itself are already known (cf. “The Pesticide Manual” 11^(th) edition, British Crop Protection Council 1997, No. 36 and also “Römpp Chemie Lexikon”, 9^(th) edition, page 2954, Georg Thieme Verlag, Stuttgart-New York, 1991).

The insecticidally and acaricidally active components which are present in the active compound combinations according to the invention in addition to the extracts from the seeds of the neem tree are likewise known. The following substances are specifically described in “The Pesticide Manual”, 11^(th) edition, British Crop Protection Council, 1997:

 (1) cypermethrin under No. 185,  (2) deltamethrin under No. 204,  (3) permethrin under No. 561,  (4) natural pyrethrum under No. 622,  (5) fenpropathrin under No. 312,  (6) cyfluthrin under No. 176,  (7) beta-cyfluthrin under No. 177,  (8) lambda-cyhalothrin under No. [lacuna]  (9) butocarboxim under No.  95, (10) pirimicarb under No. 583, (11) propoxur under No. 610, (12) methiocarb under No. 482, (13) isazophos under No. 429, (14) dimethoate under No. 243, (15) imidacloprid under No. 418, (18) acetamiprid under No.  5, (20) abamectin under No.  1, (21) diflubenzuron under No. 231, (22) buprofezin under No.  92, (23) triflumuron under No. 739, (24) diafenthiuron under No. 208, (25) fipronil under No. 323, (26) spinosad under No. 754, (27) pymetrozine under No. 615 (28) cyromazine under No. 191, (29) dicyclanil under No. 244, (30) bifenazate under No. 193, (31) hexathiazox under No. 401, (32) tebufenpyrad under No. 680 and (33) pyridaben under No. 624.

The other of the abovementioned active compounds are described in the following publications:

(16) thiacloprid EP-A-0 235 725 (17) thiamethoxam EP-A 0 580 533, (19) clothianidin EP-A 0 376 279, (34) ketoenol derivative (I) EP-A 0 528 156 and (35) ketoenol derivative (II) EP-A 0 528 156.

In addition to the extract from the seeds of the neem tree, the active compound combinations according to the invention comprise at least one of the active compounds from groups (B) to (F). Additionally, they may comprise further insecticidally and/or acaricidally active components.

The synergistic effect is particularly pronounced if the active compounds are present in the active compound combinations according to the invention in certain weight ratios. However, the weight ratios of the active compounds in the active compound combinations can be varied within a relatively wide range. In general,

from 0.02 to 20 parts by weight, preferably from 0.3 to 17 parts by weight, of active compound from group (B), from 1 to 80 parts by weight, preferably from 1.5 to 70 parts by weight, of active compound from group (C), from 1 to 60 parts by weight, preferably from 3 to 50 parts by weight, of active compound from group (D), fro 0.2 to 50 parts by weight, preferably from 0.3 to 40 parts by weight, of active compound from group (E) and from 0.2 to 60 parts by weight, preferably from 0.3 to 50 parts by weight, of active compound from group (F) are present per part by weight of extract from seeds of the neem tree.

The active compound combinations according to the invention are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which are encountered in agriculture, in gardening, in forests, in the protection of stored products and of materials and in the hygiene sector. They are active against normally sensitive and resistant species and also against all or some stages of development. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Blattaria, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Orthoptera, for example, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp.

From the order of the Thysanoptera, for example, Frankliniella occidentalis, Hercinothrips femoralis, Thrips palmi and Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Chematobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Lyriomyza spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The active compound combinations according to the invention can be used with particularly good results for controlling plant-damaging insects and acarids, such as, for example, against Tetranychus spp., Panonychu spp., Hemitarsonemus spp., Tarsonemus spp., Brevipalpus spp., Phylocoptruta spp., Aculus spp., Bryobia spp. and Eriophyes spp.

The fact that the active compound combinations are well tolerated by plants at the concentrations required for controlling insects and acarids permits the treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil. The active compound combinations according to the invention can be used for foliar application or else as seed dressing.

The active compound combinations according to the invention are usually employed in the form of compositions (formulations), for the preparation of which it is possible to use

-   -   the extracts from the seeds of the neem tree in a commercial         preparation or in the form of isolated substances and     -   the active compounds of groups (B) to (F) either as such or in         commercial preparations.

The active compound combinations according to the invention can be converted into the customary compositions (formulations), such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, microencapsulations in polymeric compounds and in coating compositions for seeds, and ULV formulations.

These formulations are produced in a known manner, for example by mixing the active compounds or active compound combinations with extenders, that is liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents include aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane, or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water. Liquefied gaseous extenders or carriers refer to those liquids which are gaseous at normal temperature and under atmospheric pressure, for example aerosol propellants, such as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic materials such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.

Tackifiers, such as carboxymethylcellulose and natural and synthetic polymers, in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 percent by weight of active compounds, preferably between 0.5 and 90%.

In the formulations, the active compound combinations according to the invention can be present as a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and as mixtures with fertilizers or plant growth regulators chelates or superabsorbers.

The active compound combinations can be employed as such, in the form of their formulations or of the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, soluble powders, granules and shaped articles. The application is carried out in a customary manner, for example by watering, spraying, atomizing, scattering, spreading, dry dressing, wet dressing, liquid dressing, slurry treatment of seeds, incrustation, implantation, injection or by foam application.

When using the active compound combinations according to the invention, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the application rates of active compound combinations are generally between 10 and 3000 g/ha, preferably between 20 and 2000 g/ha.

In the treatment of the soil, the application rates of active compound combinations are generally between 10 and 4000 g/ha, preferably between 20 and 2000 g/ha.

In the treatment of seeds, the application rates are generally between 0.01 and 50 g/kilogram of seed, preferably between 0.05 and 40 g/kilogram of seed.

The good insecticidal and acaricidal activity of the active compound combinations according to the invention is demonstrated by the examples below. Whereas the individual active compounds have weaknesses in the activity, the combinations have an activity which exceeds a simple addition of activities.

A synergistic effect of insecticides and acaricides is therefore always present when the activity of the active compound combinations exceeds the total of the activities of the active compounds when applied individually.

The expected activity for a given combination of two active compounds can be calculated according to S. R. Colby, Weeds 15 (1967), 20-22), as follows:

If

-   X is the efficacy when applying the active compound A at an     application rate of m g/ha, -   Y is the efficacy when applying the active compound B at an     application rate of n g/ha and -   E is the efficacy when applying the active compounds A and B at     application rates of m and n g/ha,     then

$E = {X + Y - {\frac{X \cdot Y}{100}.}}$

Here, the efficacy is determined in %. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

If the actual activity exceeds the calculated value, then the activity of the combination is superadditive, i.e. a synergistic effect exists. In this case, the efficacy which was actually observed must be greater than the value for the expected efficacy (E) calculated from the formula given above.

The invention is illustrated by the following examples:

EXAMPLE 1 Trialeurodes Test

To produce a suitable preparation of active compound, a commercial formulation of active compound or active compound combination is mixed with water until the desired concentration is reached.

Red sage (Lantana camara) which is heavily infested by all stages of the whitefly (Trialeurodes vaporariorum) is sprayed in intervals of 7 days in each case with a preparation of active compound at the desired application rate.

Evaluation is carried out 15 days after the second treatment. 100% means that all flies have been killed, whilst 0% means that none of the flies have been killed.

Active compounds, application rates and test results are shown in the table below.

TABLE 1 Trialeurodes test Application rate of active Active compound compound in g/ha Kill rate in % Known: Neem extract*⁾ 30 28.6 (16) thiacloprid 100 72.8 According to the found calc.**⁾ invention Neem extract*⁾ 30 + {close oversize brace} + {close oversize brace} 91.9 80.6 (16) Thiacloprid 100 *⁾The neem tree seed extract used is commercially available under the name Neem-Azal ® (from Terfolio). **⁾found = activity found calc. = activity calculated using Colby's formula

EXAMPLE 2 Trialeurodes Test

To produce a suitable preparation of active compound, a commercial formulation of active compound or active compound combination is mixed with water until the desired concentration is reached.

Red sage (Lantana camara) which is heavily infested by the whitefly (Trialeurodes vaporariorum) is sprayed in intervals of 7 days in each case with a preparation of active compound at the desired application rate.

Evaluation is carried out 15, 19 and 25 days after the second treatment. 100% means that all flies have been milled, whilst 0% means that none of the flies have been killed.

Active compounds, application rates and test results are shown in the table below.

TABLE 2 Trialeurodes test Application Kill rate in % Kill rate in % Kill rate in % rate of active 15 days after 19 days after 25 days after compound in the second the second the second Active compound g/ha treatment treatment treatment Known: Neem extract*⁾ 30 28.6 0 0 (16) Thiacloprid 100 72.8 39.5 0 According to the found calc.**⁾ found calc.**⁾ found calc.**⁾ invention Neem extract*⁾ 30 + {close oversize brace} + {close oversize brace} 91.9 80.6 82.7 39.5 70.0 0 (16) Thiacloprid 100 *⁾The neem tree seed extract used is commercially available under the name Neem-Azal ® (from Trifolio). **⁾found = activity found calc. = activity calculated using Colby's formula 

What is claimed is:
 1. An insecticidal and acaricidal composition comprising a) azadirachtin and b) spinosad or abamectin.
 2. A composition according to claim 1, comprising spinosad.
 3. A composition according to claim 1, comprising abamectin.
 4. A composition according to claim 2, comprising a weight ratio of azadirachtin to spinosad of 1:0.2 to 1:60.
 5. A composition according to claim 3, comprising a weight ratio of azadirachtin to abamectin of 1:0.2 to 1:60.
 6. A composition according to claim 2, comprising a weight ratio of azadirachtin to spinosad of 1:0.3 to 1:50.
 7. A composition according to claim 3, comprising a weight ratio of azadirachtin to abamectin of 1:0.3 to 1:50.
 8. A composition according to claim 1, which is synergistic.
 9. A composition according to claim 1, comprising 0.5 to 90% active compounds.
 10. A method of controlling pests, comprising applying a composition according to claim 1 to the pest and/or their habitat.
 11. A method according to claim 9, wherein the pests are insects or arachnids.
 12. A process for preparing a composition according to claim 1, comprising mixing a) and b) with extenders and/or surfactants. 